Textile finishing agents



Aug. 22, 1961 E. B. LAWLER ET AL TEXTILE FINISHING AGENTS 2 Sheets-Sheet1 Filed Jan. 23, 1956 WETT/NG SPEED {MODIFIED BRAVES TEST) www 0 0/ am WM? Z 0 Z i I10 w4 4 1 3 ww AA w w T Rm INVENTO/PS. EDWARD B. LAWLEP,KENNETH D. BALLOU BY ATTORNEY.

United States Patent 2,997,407 TEXTILE FINISHING AGENTS Edward B. Lawlerand Kenneth D. Ballou, Charlotte, N.C., assignors to American CyanamidCompany, New York, N. a corporation of Maine Filed Jan. 23, 1956, Ser.No. 560,706 6 Claims. (Cl. 117-1355) This invention relates to surfaceactive agents and to the wetting-out of textiles to which permanent andsemipermanent water-repellent finishes are to be applied and to thewashing, scouring, cleaning and other after-treatments of such textileshaving such finishes applied theret0.

Water-repellent finishes are normally hydrophobic in nature andnaturally resist wetting the textiles to which they are to be applied,consequently making their application and adherence to such textilesvery diificult. As a result, therefore, relatively high concentrationsof powerful wetting agents are used therewith in order to wet out thetextiles to permit the application of the water-repellent finishesthereto.

Once the Water-repellent finishes are actually applied and adhered tothe textiles, however, the continued presence of these Wetting-outagents is extremely undesirable inasmuch as they would serve to increasethe wettability of the textiles and enhance their susceptibility tospotting by water and aqueous stains, which characteristics are whollyunwanted in water-repellent textiles. Consequently, the treated textilesare normally exposed to numerous washings, cleanings, scourings or otheraftertreatments to remove the wetting-out agents which would tend todecrease the water-repellency of the textiles. This quite often involveslong and extensive washing procedures and requires the passage of thetextiles through about ten or even fifteen aqueous treating baths withintermediate nipping or squeezing-out of the treating liquid. Suchprocedures are, of course expensive, time consuming and prohibitive inthe textile industry.

The present invention is based on the discovery of a new class ofsurface active agents possessing a sufiiciently powerful wetting-outaction so as to be capable of substitution for the wetting agentspresently used in the industry for such purposes but which will notdiminish or interfere with the later water-repellency of the textileswhereby the treated textiles may be merely dried and/ or cured and thenbe capable of use as water-repellent textiles. By reason of this unusualcombination of initially good wetting properties and desirably poorlater rewetting properties, this class of wetting agents is capable ofdispersing the water-repellent finishes in the treating bath from whichit is to be applied to the textile, wetting out the textiles to permitthe facile applicability of the Water-repellent finish to the textiles,and then, following a simple drying and/or curing such as the customaryoven drying, not interfering with or detracting from the later desiredwater-repellency of materials fabricated from such textiles.

Additionally, these wetting agents are excellent for use in cleaning thefabricated water-repellent textiles after they have been worn or usedand soiled inasmuch as they can be employed to remove dirt, soil,stains, stubborn spots and the like and will then permit the re-use ofsuch textiles after a mere drying Without involving careful subsequentwashing processes.

The non-rewetting, cleaning, dispersing or wetting agents used inpracticing the processes of our invention are the ammonium soaps ofmixtuers of rosin acid or abietic acid and higher fatty acids having asuflicient chain length of from about 8 to about 22 carbon atoms ice toimpart good wetting properties to their ammonium soaps.

Additionally, it has been surprisingly discovered that, although theammonium soaps of mixtures of these acids exhibit the desiredproperties, the ammonium soap of rosin acid, per se, and the ammoniumsoap of the higher fatty acids, per se, individually do not exhibit thedesirable surface active properties required for the present invention.It is therefore believed that, when the acids are first mixed and arethen employed in the form of such a mixture to produce the ammoniumsoap, there is some sort of synergistic action taking place eitherduring the soap formation or during its later use whereby the desiredsurface active properties are obtained.

It is to be appreciated that the term rosin acid or abietic acid is notto be construed as limited to abietic acid itself which is a specificchemical compound but should be understood to cover natural or processedmaterials containing high percentages of abietic acid or abietic-typeacids including neoabietic acid, dihydroabietic acid, tetrahydroabieticacid dehydroabietic acid, dextrcpimaric acid, isodextropimaric acid,etc.

With regard to the higher fatty acids used, considerable latitude ispermitted in the selection thereof and relatively pure fatty acids maybe employed or, in the interests of economy, the commercially availablefatty acid mixtures may be used. For example, Emery 621 or Emery 622which are coconut type commercial vegetable fatty acids primarilycontaining saturated fatty acids of from 8 to about 18 carbon atoms; orEmersol 130 or Emersol 132, which are triple pressed stearic acidsprimarily containing saturated fatty acids having 16 to 18 carbon atoms;or the commercial linseed fatty acids primarily containing the 18 carbonatoms unsaturated fatty acids may be employed.

These two clases of organic acids, i.e., abietic acid and the higherfatty acids, must be used in certain definite proportions in theformation of the ammonium soap in order to obtain the combination ofproperties for the successful practice of the invention. At least about20% by weight and not more than about by weight of abietic acid must beused together with not more than about 80% or less than about 20% byweight of the fatty acids for reasons which will subsequently beexplained.

The principles of the invention will be more complete ly understood byreference to the accompanying drawings, wherein: l

FIGURE 1 shows the wetting powers of ammonium soaps of mixtures of rosinacid and coconut fatty acids in the rangesof proportions by Weight asindicated, with the total soap concentration being 0.5% (active) in theevaluation composition. The steepness and height of the ends of theU-shaped curve sharply indicated the relative ineificiency of thosecompositions containing predominant proportions (close to of eitherrosin acids or fatty acids, whereas the low central trough stronglyemphasizes the efficiency and synergistic cooperation of thosecompositions falling within the 2080% bounds of the present invention.The values noted in FIGURE 1 were obtained by means of the StandardModified Draves Test at 25 C., using cotton tape.

FIGURE 2 shows the wettingand rewetting properties of ammonium soaps ofmixtures of rosin acid and coconut fatty acids in the ranges ofproportions by weight as indicated, with the total soap concentrationbeing 12.5 grams in 1000 ml. water. The wetting times were obtained bymeans of the Standard Modified Draves Test at 25 C. using cotton tape.The rewetting results were obtained by Drop Reflectance Tests using 8oz. denim loom goods originally treated with the agent.

The Drop Reflectance Test, using 8 oz. denim loom goods, is carried outas follows: The 8 oz. denim loom goods is padded and squeezed so as togive approximately 100% wet pick-up based on the Weight of the cloth inthe test solution at the concentration listed in the appropriate tableand at a bath temperature of about 160 F. The denim is then stretched onframes and is dried at a temperature of about 220 F. for approximatelyminutes. After conditioning overnight at room temperature and standardhumidity, the denim is held taut and flat and a drop of water is placedon it and observed. The time required for this drop to soak into thedenim and to lose its tendency to refict light is measured and is calleddrop reflectance.

The general shape of the curves is to be particularly noted in FIGURE 2.The U-shaped configuration of the wetting curve is to be compared to theinverted U- shaped curve of the rewetting curve whereby it can beascertained that the optimum values for wetting times are normallyobtained within approximately the same 20-80% range as the optimumvalues for the rewetting times.

It is to be observed also that the use of the ammonium soaps either ofrosin acid, per se, or higher fatty acids, per se, in percentages closeto 100% leave much to be desired both in wetting and rewetting times.The use, however, of the 20-80% or 80-20% proportions and intermediatevalues normally leads to better and shorter wetting times with longerrewetting times.

It is therefore seen that the ammonium salts of mix-- tures of fromabout 20% to about 80% of rosin or abietic acid with from about 80 toabout 20% of oleic acid therefore will combine optimum wetting powerwith greatly decreased rewetting power and that the processes of ourinvention apply these discoveries for the treatment or aftertreatment"of textiles with water repellents to avoid the necessity of extensivewashing for removal of the wetting agent that has heretofore beoenconsidered necessary.

While it will be evident that the principles of our invention can beapplied for the cleaning of any type of water-repellent textilesincluding many of the synthetic fibers that inherently possess aconsiderable degree of water-repellency, their most important field ofutility is in the application of hydrophobic finishes to cellulosictextiles such as cotton cloth, viscose and cuprammonium rayon cloth andthe like as well as to woolen cloth. The most widely used finishes ofthis type are the heatcured mixtures of higher fatty acid amides ortheir formaldehyde reaction products with methylated methylol melaminedescribed in US. Patent No. 2,357,273 and sold commercially as Permel;the higher alkylpyridinium halides such as stearylpyridinium bromide,sold as Zelan; and the silicone finishes which are essentiallyhydroxyalkylsilicone resins. The non-rewetting ammonium soap mixtures ofthe present invention may be used with any of these or similar types ofpermanent and semi-permanent water repellents.

The water-resistant finishes of the above described types are normallyapplied to cellulosic textiles such as cotton cloth in quantities offrom about 3 to about 6%, based on the weight of the cloth, when thehighest degree of water-repellency is desired. For the so-calledspotproof or strain-proof finishes about half of these quantities areused; i.e., from about 1.5% to about 3%. The finishes are ordinarilyapplied by dispersing them in water, sometimes with the aid of anemulsifying or dispersing agent, and a'wetting agent is dissolved in thewater in the quantity necessary to make it wet out the cloth rapidly.The ammonium soap mixtures of the present invention may be used in suchbaths to replace the wetting agents previously employed, and willfunction efficiently to obtain a rapid and uniform application of thewater-proofing composition to the cloth without, however, requiring anextensive washing of the treated cloth for its removal. The ammoniumsalt mixtures are normally used in such baths in quantities of fromabout 0.1% to about 1% by weight, based on the weight of the bath, andusually in quantities of from about 0.2 to about 0.5% by weight.

After the cloth has been padded in the aqueous bath containing thewater-repellent compositions, it is normal- 1y frame-dried in an oven attemperatures within the range of about 220-400 F. for times varying fromabout 1 /2 minutes at the highest temperature to about 10-15 minutes atthe lowest temperature. The water repellent is set or cured on the clothby this heat fireatment. The cloth is then frequently scoured or cleanedin a detergent solution to remove the emulsifying agent used inpreparing the first bath as well as any unreacted or partially reactedmaterials such as incompletely cured synthetic resins that would reducethe spray rating of the finish. It is in this after-treatment orscouring procedure that the ammonium soaps of the present invention findtheir most important field of utility, for they combine good detergencywith a high degree of wetting power for the water-repellent textiles andthe scoured cloth does not require extensive rinsing in Water as isnecessary with other surface-active agents. Instead, the scoured clothis simply heated in driers at temperatures above 220 F. and preferablybetween about 250 and 400 F. for the time necessary to dry it to thedesired extent, which is usually within the range of about 15-10minutes.

Quantities of the ammonium soap mixtures of the present invention withinthe range of about 0.1% to 1%, and usually about 02-06% on the weight ofthe bath are usually employed in these scouring processes. The scouringbath may contain other ingredients if desired such as 01-05% of sodiumcarbonate, or preferably 0.21.0% ammonia, as ammonium hydroxide, but, ofcourse, should not contain other Wetting agents of the type whichdecrease the Water resistance of the cloth. The scouring is preferablycarried out at elevated temperatures on the order of l30-l60 F.,although the particular scouring procedures used will of course varywith the type of cloth being treated and the impurities that must beremoved. We have found that the addition of about 0.5-l% by weight ofammonia to scouring baths containing the ammonium soaps of our inventionwill increase the effectiveness of these Wetting agents in many cases.

The invention will be further described and illustrated by the followingexamples which show the application of the principles thereof toillustrative water-proofing treatments for textiles. It will beunderstood, however, that the invention in its broader aspects is notlimited to the detailed quantities and procedures shown in theseexamples, the scope of the invention being defined by the appendedclaims.

Example 1 Surface active formulations having the following compositionsby weight were prepared, the parts being given by weight.

l 1 i 2 1 3 l 4 5 i 6 855 855 855 855 855 855 Gum Rosin 10D 60 40 20 0Oleic Acid.- O 20 40 60 80 Ammonia (26%).... 45 45 45 45 45 45 The rosinand an equal weight of water were heated together at about 100 C. untilthe rosin was melted; the oleic acid was then added with stirring at thesame temperature and the stirring was continued until the mixture washomogeneous. The batches were then cooled to room temperature, theammonia was added slowly and the remainder of the water was stirred in.

The wetting power of the compositions was determined in water solutionscontaining 0.56% and 0.28% by weight (active) of the ammonium soaps bythe Standard Draves sinking test.

Rewetting times were determined by the AATCC tentative test method 2752which consists essentially in depositing a Water droplet on fabricimpregnated uniformly with a known quantity of the material under testand measuring the time in minutes before it is absorbed by the cloth.Eight ounce denim was packed in a 0.56% solution of the soaps (or 5% ofthe compositions), passed through squeeze rolls set for 100% pickup andoven dried at 220 F. and then tested. Wetting times (secs).

On the basis of the test results of Example 1, a 100 lb. batch of asurface active composition was prepared from a mixture containing byweight of red oil (commercial oleic acid), 10% gum rosin, 10% of aqueousammonia containing 28% NH, and 5% of isopropyl alcohol as a clarifyingagent. The rosin and an equal weight of water were charged into ajacketed kettle, heated to boiling and maintained at the boil until therosin was completely melted. The red oil was added slowly with stirringat the same temperature and the batch was cooled to room temperatureafter it had become homogeneous. With continued stirring the alcohol wasadded followed by addition of the ammonia and when the ammonium soapformation was complete the remaining water was added. The finalcomposition contained 22.6% solids.

The wetting power of the composition for cloth treated with a commercialwater-repellent 'finish was measured in comparison with a nonionicwetting agent composition in wide commercial use for this purpose. Thewetting power was measured by determining the sinking times for 1" x 1"squares of the treated cloth (8 oz. denim) in aqueous solutionscontaining 0.5% of sodium carbonate g wetting agents used commerciallyfor scouring cloth after the application of permanent water-repellentfinishes thereto. The tests were made by measuring the sinking time of1" 'x 1" squares of cotton poplin treated with Permel, which is .apermanent water-repellent finish having the composition and method ofapplication 'described in US. Patent No. 2,491,249 dated December 13,1949. The test results (seconds) were as follows:

. NHfSoap Igepal CO Triton W-30, Cone, Percent Compositions, 633,,33.3%38% solids 18% solids solids Rewetting Times and dried at 220 F 10 3 5These results show that the ammonium oleyl rosinate compositions of thepresent invention have wetting and detergent properties comparable tothose of the inost wldely used commercial wetting agents for clothcontaining permanent water-repellent finishes, but possess greatlyreduced wetting power thereafter (rewetting). The ammonium oleylrosinate detergents can therefore be used successfully 'as scouringagents for cloth pretreated with Permel, Zelan,stearoguanamine-containirig compositions, silicone resins ir'iixt-iir'esiif'ifiethyl ated 'methylgl melamine with higher aliphatic alcohols andother known or approved permanent and semi-permanent water-repellentfinishes without, however, resorting to an extensive scouring to removethe wetting agent from the finish. V

- Example 3 Six surface active compositions having the'proportions setforth in'Ex-ample 1 were prepared, using different fatty acids asindicated.

' RATIO OF ACID COMPONENTS .IN FORMULATIONS (BY WEIGHT) plus the wettingagents in the concentrations indicated 1 2 3 4 5 6 111 the followmgtable:

Fatty Acid 100 80 60 40 20 0 tt Time, s c B03111 Ac 0 20 40 60 80 100 Aent Cone, Percent x g HN; Soap Commercial Fatty Acid 0on0. Wetting Speed(Modifiedpraves Test) Composition WettingAgent Tape S g Tune 1. 4 1.0 Conut 1 g 23 101 1.4 1.5 3.0 2.8 Fatty 9s 94 '10s 5.0 62 51 .83 101 21.0129 117 172 26 34 49 101 Fatty Acids 139 Rewettmg tunes were determinedon batches of the same cloth padded in baths containing 0.5% of sodiumcarbonate plus 0.63% of the detergents under test. The rewetting time ofthe cloth impregnated with 0.63% of ammonium oleyl rosinate wasexcellent and was more than 360 seconds; the rewetting time for thecloth impregnated with the commercial detergent composition was tooshort and was only 20 seconds.

The commercial wetting agent composition used as a standard ofcomparison in this test was a mixture of 12% by weight of Nonic 218which is the condensation product of approximately 9 mols of ethyleneoxide with 1 mol of l-dodecyl mercaptan, 6% by weight of Ultrawet K, adodecyl benzene sodium sulfonate, and 82% by weight of water.

Comparative tests were also made against Igepal CO 633 and Triton W-30,both of which are well known 1 (See Figure 1 of drawings.)

Example 4 The surface active compositions ofExample 1 were prepared inthe concentrations shown therein but using tall oil rosin acids (Acintol R) in conjunction with the "oleic' acid. -These rosin acids contained36% abietic acid, 16% neoabietic acid, 13% dihydroabietic acid, 12%tetrahydroabietic acid, 7% dextropimaric acid, 7% isodextropimaric acidand 5% dehydroabietic acid. It is to be observed that these rosin acidsare similar to those occurring in wood and gum rosin. The wetting andrewetting times were comparable to those of the composition of Example1.

Example 6 Example 5 was repeated using Acintol C containing 51% rosinacids, 2.5% palmitic acid 20% oleic acid, 18.5% linoleic acid, 0.5%linolenic acid and 7.1% unsaponifiable acid. The wetting and rewettingproperties compared very favorably with the properties of thecompositions of Example 1.

Example 7 .Example 5 was repeated using Acintol D containing 32% rosinacids, 6% linoleic (conjugated) acid, 25% linoleic (non-conjugated)acid, 34% oleic acid and 2% 'palmitic acid. The wetting and rewettingproperties compared very favorably with the positions of Example 1.

The following table sets forth numerically the Wetting properties of thecomand rewetting activity of ammonium soaps of mixtures of a fatty acidsand rosin acids referred to more generally elsewhere. TABLE 1 [byweight] Gum Rosin 2O Acintol D 20 Acintol R Oleic Acid 10 Stearic AcidCoconut Fatty A nid Isopropanol 5 5 5 Ammonia (28%) 10 10 10 Water 65 6565 Percent Gone. Wetting SpeeSd (Modified Draves Test) Tape inking Time(sec.)

RewettingiSgeed (8 oz. denim loom goods) Drop ectance Duration (mms.)

Example 8 ing and curing process, did not exert any deleterious Thewetting and rewetting properties 1 of various rosincoconut fatty acidammonium soaps were evaluated as follows:

' The Tape Wetting Times in seconds at 25 C. using a cotton tape in 50grams of agent in 1000 ml. water in the Standard Modified Draves Testwere as follows:

1 See Figure 2 of drawings.

Example 9 Treating baths for applying water-repellent finishes wereprepared as follows:

Permel Resin B- Aerotcx Accelerator AS Immersion: 1 dip; 1 nip onto 5.5oz. cotton poplin.

Pressure: 3.5 tons.

Expression: 80%.

Dry at: 225 F.

Cure at: 350 F. for 1.5 minutes.

The product of Example 2 markedly accelerated the wetting-out of thecotton poplin during the application of the water-repellent finishindicated and, after the dryeifect on the water-repellency of the cottonpoplin.

The following table sets forth the normal average compositions by weightof the ranges of the various fatty acid mixtures referred to in thespecification.

Although several specific examples of the inventive concept have beendescribed, the same should not be construed as limited thereby nor tothe specific substances mentioned therein but to include various othercompounds of equivalent constitution as set forth in the claims appendedhereto. It is understood that any suitable changes, modifications andvariations may be made without departing from the spirit and scope ofthe invention.

We claim:

1. A method of applying a water-repellent composition to textiles whichcomprises Wetting out said textiles in an aqueous dispersion of saidwater-repellent composition by the wetting action of ammonium soaps of amixture of from about 20% to about 80% by weight of abietic acid andfrom about 80% to about 20% by weight of fatty acids of from about 8 toabout 22 carbon atoms and thereby applying the water repellent to thetextiles and drying the textiles containing the applied water-repellentcomposition by heating them at temperatures of from about 220 to about400 F.

2. A method of applying a water-repellent composition to textiles whichcomprises wetting out said textiles in an aqueous dispersion of saidwater-repellent composition containing from about 0.1% to about 1% byweight of a wetting-out agent comprising ammonium soaps of a mixture offrom about 20% to about by weight of abietic acid and from about 80% toabout 20% by weight of fatty acids of from about 8 to about 22 carbonatoms and thereby applying the water repellent to the textiles anddrying the textiles containing the applied 9 water-repellentcompositions by heating them at temperatures of from about 220 to about400 F.

3. A method of applying a water-repellent composition to textiles whichcomprises Wetting out said textiles in an aqueous dispersion of saidwater-repellent composition by the wetting action of ammonium soaps of amixture of from about 20% to about 80% by Weight of abietic acid andfrom about 80% to about 20% by weight of coconut fatty acids of fromabout 8 to about 18 carbon atoms and thereby applying the Waterrepellent to the textiles and drying the textiles containing the appliedwater-repellent composition by heating them at temperatures of fromabout 220 to about 400 F.

4. A method of applying a water-repellent composition to textiles whichcomprises Wetting out said textiles in an aqueous dispersion of saidwater-repellent composition by the wetting action of ammonium soaps of amixture of from about 20% to about 80% by Weight of abietic acid andfrom about 80% to about 20% by weight of linseed fatty acids of fromabout 16 to about 18 carbon atoms and thereby applying the waterrepellent to the textiles and drying the textiles containing the appliedwaterrepellent composition by heating them at temperatures of from about220 to about 400 F.

5. A method of applying a water-repellent composition to textiles whichcomprises wetting out said textiles in an aqueous dispersion of saidwater-repellent composition by the wetting action of ammonium soaps of amixture of from about 20% to about 80% by Weight of abietic acid andfrom about 80% to about 20% by Weight of oleic acid and thereby applyingthe water repellent to the textiles and drying the textiles containingthe applied 1O water-repellent composition by heating them attemperatures of from about 220 to about 400 F.

6. A method of applying a water-repellent composition to textiles whichcomprises: Wet-ting out said textiles in an aqueous dispersion of saidWater-repellent composition by the wetting action of ammonium soaps of amixture of from about 20% to about by weight of abietic acid and fromabout 80% to about 20% by weight of stearic acid and thereby applyingthe water repellent to the textiles and drying the textiles containingthe applied water-repellent composition by heating them at temperaturesof from about 220 to about 400 F.

References Cited in the file of this patent UNITED STATES PATENTS1,362,658 Willford Dec. 21, 1920 1,732,729 Phair Oct. 22, 1929 2,052,170Engelmann Aug. 25, 1936 2,069,823 Driesen Feb. 9, 1937 2,191,982 DoserFeb. 27, 1940 2,304,367 Morgan Dec, 6, 1942 2,350,548 D'eLaney June 6,1944 2,362,894 Epstein Nov. 14, 1944 2,489,473 Zerner Nov. 29, 1949FOREIGN PATENTS 2,527 Great Britain Oct. 28, 1856 OTHER REFERENCES

1. A METHOD OF APPLYING A WATER-REPELLENT COMPOSITION TO TEXTILES WHICHCOMPRISES WETTING OUT SAID TEXTILES IN AN AQUEOUS DISPERSION OF SAIDWATER-REPELLENT COMPOSITION BY THE WETTING ACTION OF AMMONIUM SOAPS OF AMIXTURE OF FROM ABOUT 20% TO ABOUT 80% BY WEIGHT OF ABIETIC ACID ANDFROM ABOUT 80% TO ABOUT 20% BY WEIGHT OF FATTY ACIDS OF FROM ABOUT 8 TOABOUT 22 CARBON ATOMS AND THEREBY APPLYING THE WATER REPELLENT TO THETEXTILES AND DRYING THE TEXTILES CONTAINING THE APPLIED WATER-REPELLENT